108-41-8Relevant articles and documents
Evidence for Generation of the Unsaturated Sila-acetate Species Me(O-)Si=O by Dissociation of the Silanediolate Dianion m-ClC6H4CH2SiMe(O-)2
Chmielecka, Jadwiga,Chojnowski, Julian,Eaborn, Colin,Stancyzk, Wlodimierz A.
, p. 1337 - 1338 (1987)
Kinetic studies indicate that in the cleavage of m-ClC6H4CH2SiMe(OH)2 by NaOH in Me2SO-H2O there is a major contribution by unimolecular dissociation of the dianion m-ClC6H4CH2SiMe(O-)2 to give the acetate ion analogue Me(O-)Si=O.
Thermodynamic Analysis of Isomerization Equilibria of Chlorotoluenes and Dichlorobenzenes in a Biphasic Reaction Systems Containing Highly Acidic Chloroaluminate Melts
Verevkin, Sergey P.,Messner, Julia,Emel'Yanenko, Vladimir N.,Gantman, Mikhail G.,Schulz, Peter S.,Wasserscheid, Peter
, p. 13152 - 13160 (2016)
Thermodynamics and kinetics of the isomerization of chlorotoluenes and dichlorobenzene to the technically desired meta-isomers have been studied in the presence of highly acidic chloroaluminate melts with alkali metal and organic imidazolium cations. Enthalpies of four isomerization processes in reacting systems of chlorotoluenes and dichlorobenzene were obtained from temperature dependencies of the corresponding equilibrium constants in the liquid phase. Experimental reaction enthalpies, enthalpies of vaporization, and absolute vapor pressures of chlorotoluenes and dichlorobenzene have been used for the validation of quantum-chemical methods to predict thermodynamic functions of the four reactions under study successfully. Values of the standard Gibbs energies of formation, standard enthalpies and entropies of formation of chlorotoluenes and dichlorobenzenes in the liquid and in the gas phase have been derived. These values allow optimization of liquid-liquid biphasic manufacturing technologies for halogen-substituted benzenes.
Chemistry of superacids: 35. * NO2Cl-3MXN systems: Superelectrophilic aprotic nitrating agents for deactivated aromatics
Olah,Orlinkov,Ramaiah,Oxyzoglou,Prakash
, p. 924 - 927 (1998)
Superelectrophilic nitration of deactivated aromatics with NO2Cl-3MXn complexes in aprotic nonpolar solvents such as CH2Cl2 makes it possible to obtain the corresponding nitro derivatives in good to almost quantitative yields under mild conditions.
Two efficient methods for the preparation of 2-chloro-6-methylbenzoic acid
Daniewski, Andrzej R.,Liu, Wen,Puentener, Kurt,Scalone, Michelangelo
, p. 220 - 224 (2002)
Two efficient methods for the preparation of 2-chloro-6-methylbenzoic acid were developed: one based on nucleophilic aromatic substitution and the other based on carbonylation. In the first approach, 2-chloro-6-fluorobenzaldehyde was converted to its n-butylimine, then treated with 2 equiv of methylmagnesium chloride in THF to give, after hydrolysis, 2-chloro-6-methylbenzaldehyde. Subsequent oxidation of this compound gave the title compound in 85% overall yield. In the second approach, 3-chloro-2-iodotoluene was efficiently carbonylated in methanol to give methyl 2-chloro-6-methylbenzoate, which after hydrolysis afforded the title compound in 94% yield (84% yield after recrystallization). The carbomethoxylation proceeded smoothly even at a high substrate-to-Pd ratio of 10 000. Both methods do not require isolation of intermediates and are suitable for the preparation of kilogram quantities of 2-chloro-6-methylbenzoic acid.
Deep compositional understanding of TBA: AlCl3 ionic liquid for its applications
Bhakthavatsalam, Vishnupriya,Chandra, Sudeshna,Choudhury, Rudra Prosad,Lande, Sharad V.,Pradhan, Jeevan,Sakhalkar, Mangesh
, (2020/07/31)
Chloroaluminate ionic liquids (ILs) have been immensely used as homogeneous catalyst in Friedel-Crafts reaction. We have recently synthesized chloroaluminate ILs by reacting aluminium chloride with a hydrophobic neutral ligand i.e. tributylamine (TBA:AlCl3). The current study elaborates on the investigations of the composition of the ionic liquids at various stages of their formation. The ionic liquids were synthesized using various mole ratios of tributyl amine and aluminium chloride in range of 1:1 to 1:2.3, in presence of an aromatic solvent in a one pot reaction. Various characterization techniques like Mass spectrometry, 27Al Nuclear Magnetic Resonance, 31P Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopy were used to elucidate the formation of various moieties of the TBA:AlCl3 Ionic Liquid. This study also elaborates on the investigations of the cationic and anionic moieties and their structure-property relationship for various applications. Various Friedel-Crafts reaction of industrial importance were performed using the ionic liquid having (Al2Cl7)?moiety to assess its performance and compared with conventional processes. The synthesized products were characterised by sophisticated analytical techniques like 1H NMR, 13C NMR, FTIR, GC–MS, GC-FID, to name a few. This class of ionic liquids also have importance in various electrochemical applications like aluminium deposition and aluminium batteries.
Catalytic Reductions Without External Hydrogen Gas: Broad Scope Hydrogenations with Tetrahydroxydiboron and a Tertiary Amine
Korvinson, Kirill A.,Akula, Hari K.,Malinchak, Casina T.,Sebastian, Dellamol,Wei, Wei,Khandaker, Tashrique A.,Andrzejewska, Magdalena R.,Zajc, Barbara,Lakshman, Mahesh K.
supporting information, p. 166 - 176 (2020/01/02)
Facile reduction of aryl halides with a combination of 5% Pd/C, B2(OH)4, and 4-methylmorpholine is reported. Aryl bromides, iodides, and chlorides were efficiently reduced. Aryl dihalides containing two different halogen atoms underwent selective reduction: I over Br and Cl, and Br over Cl. Beyond these, aryl triflates were efficiently reduced. This combination was broadly general, effectuating reductions of benzylic halides and ethers, alkenes, alkynes, aldehydes, and azides, as well as for N-Cbz deprotection. A cyano group was unaffected, but a nitro group and a ketone underwent reduction to a low extent. When B2(OD)4 was used for aryl halide reduction, a significant amount of deuteriation occurred. However, H atom incorporation competed and increased in slower reactions. 4-Methylmorpholine was identified as a possible source of H atoms in this, but a combination of only 4-methylmorpholine and Pd/C did not result in reduction. Hydrogen gas has been observed to form with this reagent combination. Experiments aimed at understanding the chemistry led to the proposal of a plausible mechanism and to the identification of N,N-bis(methyl-d3)pyridin-4-amine (DMAP-d6) and B2(OD)4 as an effective combination for full aromatic deuteriation. (Figure presented.).
Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds
Stache, Erin E.,Ertel, Alyssa B.,Rovis, Tomislav,Doyle, Abigail G.
, p. 11134 - 11139 (2018/11/21)
Despite the prevalence of alcohols and carboxylic acids as functional groups in organic molecules and the potential to serve as radical precursors, C-O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen-centered nucleophile. We show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H atom trapping to afford the deoxygenated products. Using the same method, we demonstrate access to synthetically versatile acyl radicals, which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge C-O, C-N, and C-C bonds in a single step.
A process for preparing O-toluene
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Paragraph 0015-0018, (2018/10/11)
The present invention provides a process for preparing dichloro toluene, relates to the field of preparation of organic intermediates. The invention relates to 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene in more than one type of raw materials, supported palladium as the catalyst, a fixed bed continuous reaction preparation of O-toluene. This invention uses the industrial by-product 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene as the raw materials, supported palladium catalyst good selectivity, long-time use, O-chlorotoluene high yield.
Decarbonylation of Aromatic Aldehydes and Dehalogenation of Aryl Halides Using Maghemite-Supported Palladium Catalyst
Ajda?i?, Vladimir,Nikoli?, Andrea,Simi?, Stefan,Manojlovi?, Dragan,Stojanovi?, Zoran,Nikodinovic-Runic, Jasmina,Opsenica, Igor M.
, p. 119 - 126 (2017/12/27)
A facile decarbonylation reaction of a variety of aromatic and heteroaromatic aldehydes using maghemite-supported palladium catalyst has been developed. The magnetic properties of catalyst facilitated an easy and efficient recovery of the catalyst from the reaction mixture using an external magnet. It was found that the catalyst could be reused up to four consecutive catalytic runs without a significant change in activity. In addition, the catalyst was also very effective in the dehalogenation of aryl halides. This is the first report on efficient utilization of directly immobilized Pd on maghemite in decarbonylation and dehalogenation reactions.
Substd. photoisomerization arom. compd. method
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Paragraph 0065, (2017/01/02)
Isomerizing substituted aromatic compounds (I), comprises carrying out isomerization in the presence of a salt melt, which contains a metal compound (II) and at least one metal compound (III). Isomerizing substituted aromatic compounds of formula (Ar1-R n) (I) or their mixtures, comprises carrying out isomerization in the presence of a salt melt, which contains a metal compound of formula ([M1][X1] m 1) (II) and at least one metal compound of formula ([M2][X2] m 2) (III). Ar1 : n-valent aryl radical; R : halo, alkyl, fluoroalkyl, aryl, alkyl-aryl or amino; M1 : Al, Ga, In, Cu, Fe, Co or Ni; X1, X2 : halo, preferably Cl or Br; M2, m2 : alkaline earth metal or alkali metal, where M2 is preferably Li, Na, or K; m1 : Al, Ga, In, Fe(III), Co, Ni or Cu(II); and n : >= 2, preferably 2.